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RU2008129062A - SUBSTANCES OF CATALYSTS USED IN FISCHER-TROPSH SYNTHESIS AND THEIR APPLICATION - Google Patents

SUBSTANCES OF CATALYSTS USED IN FISCHER-TROPSH SYNTHESIS AND THEIR APPLICATION Download PDF

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RU2008129062A
RU2008129062A RU2008129062/04A RU2008129062A RU2008129062A RU 2008129062 A RU2008129062 A RU 2008129062A RU 2008129062/04 A RU2008129062/04 A RU 2008129062/04A RU 2008129062 A RU2008129062 A RU 2008129062A RU 2008129062 A RU2008129062 A RU 2008129062A
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catalyst
porous body
synthesis gas
catalytic substrate
mixtures
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RU2008129062/04A
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RU2412926C2 (en
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Арнольд Марсель Альбер РУТЬЕ (NL)
Арнольд Марсель Альбер РУТЬЕ
Франсискус Йоханнес Мария СХРАУВЕН (NL)
Франсискус Йоханнес Мария СХРАУВЕН
Герардус Петрус Ламбертус НИСЕН (NL)
Герардус Петрус Ламбертус НИСЕН
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Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL)
Шелл Интернэшнл Рисерч Маатсхаппий Б.В.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors
    • C10G2/342—Apparatus, reactors with moving solid catalysts
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    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00654—Controlling the process by measures relating to the particulate material
    • B01J2208/00672—Particle size selection
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    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

1. Каталитическая подложка, содержащая катализатор синтеза Фишера-Тропша или предшественник катализатора и пористое тело, которое имеет размер 1 - 50 мм, предпочтительно 1-30 мм, и каталитическая подложка имеет внутреннюю пористость 50 - 95%. ! 2. Каталитическая подложка по п.1, в которой пористое тело имеет форму проволочной ткани, ячеистой структуры, монолита, губки, сетки, решетки, конструкции из фольги или форму тканого каркаса. ! 3. Каталитическая подложка по пп.1 или 2, в которой пористое тело состоит из материала, выбранного из группы, состоящей из тугоплавких оксидов, металлов или их смесей. ! 4. Каталитическая подложка по п.3, в которой пористое тело состоит из тугоплавкого оксидного материала, выбранного из группы, состоящей из диоксида титана, диоксида кремния, диоксида циркония, оксида алюминия и их смесей. ! 5. Каталитическая подложка по п.3, в которой пористое тело состоит из нержавеющей стали. ! 6. Каталитическая подложка по п.1, в которой объем пустот внутри каталитической подложки больше, чем 60%, предпочтительно больше, чем 70%, более предпочтительно больше, чем 80%. ! 7. Каталитическая подложка по п.1, в которой катализатор или предшественник катализатора расположен в виде слоя на пористом теле, причем указанный слой предпочтительно имеет среднюю толщину от 1 до 300 мкм, предпочтительно от 5 до 200 мкм. ! 8. Каталитическая подложка по п.1, в которой доля катализатора от объема каталитической подложки составляет, по меньшей мере, 1% предпочтительно, по меньшей мере, около 4% от объема каталитической подложки. ! 9. Способ получения обычно газообразных, обычно жидких и необязательно обычно твердых углеводородов из синтез-газа в трехфазн1. A catalyst support comprising a Fischer-Tropsch synthesis catalyst or a catalyst precursor and a porous body which has a size of 1 - 50 mm, preferably 1 - 30 mm, and the catalyst support has an internal porosity of 50 - 95%. ! 2. The catalytic support according to claim 1, wherein the porous body is in the form of a wire cloth, a honeycomb structure, a monolith, a sponge, a mesh, a lattice, a foil structure, or a woven frame form. ! 3. Catalytic support according to claim 1 or 2, wherein the porous body consists of a material selected from the group consisting of refractory oxides, metals or mixtures thereof. ! 4. The catalytic support according to claim 3, wherein the porous body consists of a refractory oxide material selected from the group consisting of titanium dioxide, silica, zirconia, alumina, and mixtures thereof. ! 5. The catalytic support according to claim 3, wherein the porous body is made of stainless steel. ! 6. The catalyst support according to claim 1, wherein the void volume within the catalyst support is greater than 60%, preferably greater than 70%, more preferably greater than 80%. ! 7. The catalyst support according to claim 1, wherein the catalyst or catalyst precursor is arranged as a layer on the porous body, said layer preferably having an average thickness of from 1 to 300 μm, preferably from 5 to 200 μm. ! 8. The catalyst support according to claim 1, wherein the proportion of catalyst to the volume of the catalyst support is at least 1%, preferably at least about 4% of the volume of the catalyst support. ! 9. A method for producing usually gaseous, usually liquid and optionally usually solid hydrocarbons from synthesis gas in a three-phase

Claims (13)

1. Каталитическая подложка, содержащая катализатор синтеза Фишера-Тропша или предшественник катализатора и пористое тело, которое имеет размер 1 - 50 мм, предпочтительно 1-30 мм, и каталитическая подложка имеет внутреннюю пористость 50 - 95%.1. A catalyst support comprising a Fischer-Tropsch synthesis catalyst or a catalyst precursor and a porous body that has a size of 1-50 mm, preferably 1-30 mm, and the catalyst support has an internal porosity of 50-95%. 2. Каталитическая подложка по п.1, в которой пористое тело имеет форму проволочной ткани, ячеистой структуры, монолита, губки, сетки, решетки, конструкции из фольги или форму тканого каркаса.2. The catalytic substrate according to claim 1, in which the porous body has the form of a wire cloth, a cellular structure, a monolith, a sponge, a mesh, a lattice, a foil structure or the shape of a woven frame. 3. Каталитическая подложка по пп.1 или 2, в которой пористое тело состоит из материала, выбранного из группы, состоящей из тугоплавких оксидов, металлов или их смесей.3. The catalytic substrate according to claims 1 or 2, in which the porous body consists of a material selected from the group consisting of refractory oxides, metals or mixtures thereof. 4. Каталитическая подложка по п.3, в которой пористое тело состоит из тугоплавкого оксидного материала, выбранного из группы, состоящей из диоксида титана, диоксида кремния, диоксида циркония, оксида алюминия и их смесей.4. The catalytic substrate according to claim 3, in which the porous body consists of a refractory oxide material selected from the group consisting of titanium dioxide, silicon dioxide, zirconia, aluminum oxide and mixtures thereof. 5. Каталитическая подложка по п.3, в которой пористое тело состоит из нержавеющей стали.5. The catalytic substrate according to claim 3, in which the porous body consists of stainless steel. 6. Каталитическая подложка по п.1, в которой объем пустот внутри каталитической подложки больше, чем 60%, предпочтительно больше, чем 70%, более предпочтительно больше, чем 80%.6. The catalytic substrate according to claim 1, in which the volume of voids inside the catalytic substrate is more than 60%, preferably more than 70%, more preferably more than 80%. 7. Каталитическая подложка по п.1, в которой катализатор или предшественник катализатора расположен в виде слоя на пористом теле, причем указанный слой предпочтительно имеет среднюю толщину от 1 до 300 мкм, предпочтительно от 5 до 200 мкм.7. The catalytic substrate according to claim 1, in which the catalyst or catalyst precursor is located in the form of a layer on a porous body, said layer preferably having an average thickness of from 1 to 300 μm, preferably from 5 to 200 μm. 8. Каталитическая подложка по п.1, в которой доля катализатора от объема каталитической подложки составляет, по меньшей мере, 1% предпочтительно, по меньшей мере, около 4% от объема каталитической подложки.8. The catalytic substrate according to claim 1, in which the proportion of catalyst from the volume of the catalytic substrate is at least 1%, preferably at least about 4% of the volume of the catalytic substrate. 9. Способ получения обычно газообразных, обычно жидких и необязательно обычно твердых углеводородов из синтез-газа в трехфазном реакторе, который включает стадии:9. A method for producing typically gaseous, usually liquid, and optionally usually solid hydrocarbons from synthesis gas in a three-phase reactor, which comprises the steps of: (i) введение синтез-газа в реактор; и(i) introducing synthesis gas into the reactor; and (ii) контактирование синтез-газа с нестационарным катализатором для того, чтобы каталитически превратить синтез-газ при повышенной температуре с целью получения обычно газообразных, обычно жидких и необязательно обычно твердых углеводородов из синтез-газа; причем катализатор на стадии (ii) расположен во множестве пористых тел, имеющих размер 1-50 мм, предпочтительно размер 1-30 мм, и таким образом, образуются катализаторные подложки, и где указанные катализаторные подложки обладают внешней пористостью в реакторе in situ 5 - 60%, и пористостью внутри катализаторной подложки 50-95%.(ii) contacting the synthesis gas with a non-stationary catalyst in order to catalytically convert the synthesis gas at an elevated temperature in order to obtain typically gaseous, usually liquid and optionally usually solid hydrocarbons from the synthesis gas; wherein the catalyst in step (ii) is located in a plurality of porous bodies having a size of 1-50 mm, preferably a size of 1-30 mm, and thus catalyst supports are formed, and wherein said catalyst supports have external porosity in an in situ reactor of 5-60 %, and porosity within the catalyst support 50-95%. 10. Способ по п.9, который включает катализаторные подложки, заявленные в пп.1-8.10. The method according to claim 9, which includes a catalyst substrate, as claimed in claims 1 to 8. 11. Способ по п.9 или 10, в котором активный компонент катализатора выбирают из группы, состоящей из кобальта, железа, рутения и их смесей, предпочтительно кобальта.11. The method according to claim 9 or 10, in which the active component of the catalyst is selected from the group consisting of cobalt, iron, ruthenium and mixtures thereof, preferably cobalt. 12. Способ по п.9, в котором стадия (ii) дополнительно включает в себя применение промотора, который выбирают из группы, состоящей из циркония, марганца, ванадия, рения, платины, палладия и их смесей, предпочтительно марганца, ванадия и их смесей.12. The method according to claim 9, in which stage (ii) further includes the use of a promoter that is selected from the group consisting of zirconium, manganese, vanadium, rhenium, platinum, palladium and mixtures thereof, preferably manganese, vanadium and mixtures thereof . 13. Применение катализаторных подложек по пп.1-8 в способе получения обычно газообразных, обычно жидких и необязательно твердых углеводородов из синтез-газа, который включает в себя стадии:13. The use of catalyst substrates according to claims 1 to 8 in a method for producing usually gaseous, usually liquid and optionally solid hydrocarbons from synthesis gas, which includes the steps of: (i) подача синтез-газа; и(i) supply of synthesis gas; and (ii) контактирование синтез-газа с каталитическим материалом для того, чтобы каталитически превратить синтез-газ со стадии (i) при повышенной температуре и давлении с целью получения обычно газообразных, обычно жидких и необязательно обычно твердых углеводородов. (ii) contacting the synthesis gas with the catalytic material in order to catalytically convert the synthesis gas from step (i) at elevated temperature and pressure to produce typically gaseous, usually liquid, and optionally usually solid hydrocarbons.
RU2008129062/04A 2005-12-16 2006-12-14 Catalyst systems used in fischer-tropsch synthesis and use thereof RU2412926C2 (en)

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EP1960325A1 (en) 2008-08-27
AU2006325210B2 (en) 2010-08-26
US20090012189A1 (en) 2009-01-08
RU2412926C2 (en) 2011-02-27
WO2007068732A1 (en) 2007-06-21
JP2009519124A (en) 2009-05-14
AU2006325210B8 (en) 2010-09-23
AU2006325210A1 (en) 2007-06-21
MY148113A (en) 2013-02-28

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